JP3233939B2 - Method using dimerization catalyst and alkylaluminum alkoxide - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to catalysts useful for dimerizing α-olefins. More specifically, the present invention provides
An alkylaluminum alkoxide catalyst for achieving olefin dimerization.

BACKGROUND OF THE INVENTION Organoaluminum compounds have long been used in the preparation of catalysts such as, for example, Ziegler type catalysts. The preparation of these catalysts is described, for example, in U.S. Pat.
No. 6 discloses it. It is based on the ability of the organoaluminum compound to act as a reducing agent to reduce the transition metal to a zero-balance state.

U.S. Pat. No. 2,959,607 discloses that at substantially atmospheric pressure, the presence of cobalt chloride in the presence of at least a stoichiometric amount of triisobutyl aluminum
To prepare an aluminum alkyl containing at least one n-octyl group. Said catalyst obviously acts as both an isomerization catalyst and a displacement catalyst in this way. Aluminum alkyls can be oxidized and hydrolyzed to form octanol-1.

U.S. Patent No. 2,962,513, with 100 to 300% stoichiometric amount excess of C ₃ or higher of α- olefins, from ethyl aluminum compounds, by catalytic olefin metathesis of ethylene, more aluminum alkyl long chain A method of making is disclosed. The method can be carried out under atmospheric pressure, from 50 to
At a temperature of 200 ° C., salts and oxides of Group VIII metals are used as catalyst. In this reaction, ethylene is released.

U.S. Pat.No. 3,784,623 discloses the addition of inhibitors or catalyst deactivators to the process to adjust the increasing trend associated with catalytic displacement of the alpha-olefin to isomerize to internal olefin. ing.

U.S. Pat. No. 4,973,788 discloses trialkylaluminum catalysts that are useful for dimerizing various vinyl olefin monomers. The term "vinyl
“Olefin” has the same meaning as “α-olefin” and is used interchangeably. This patent specifically mentions the use of low levels of organoaluminum catalyst. The reason for this is that higher amounts promote the formation of undesired monomers and dimeric internal olefins.

According to the present invention, (Wherein, R ¹ and R ² are the same or different and are hydrogen or alkyl, m is an integer of 0 to 18;
Wherein R ² is not hydrogen when R is 0). The method comprises:
At a temperature of 100 ° C. to 250 ° C., consisting of a mixture of aluminum compound (s) and of the formula R ⁴ _n Al (OR ⁵ ) _p , wherein R ⁴ and R ⁵ are the same or different and are alkyl And n is a value between 0.75 and 2.75, p has a value between 0.25 and 2.25, and the sum of n and p is 3) in the presence of a catalytically effective amount of a catalyst composition having And dimerizing the alpha olefin.

Furthermore, the present invention is an aluminum compound (s) consist of a mixture of and wherein _{^{R 4 n Al (OR 5)}} p ( wherein, R ⁴
And R ⁵ are the same or different and are alkyl,
n is a number from 0.75 to 2.75, p is a number from 0.25 to 2.25, and the sum of n and p is 3).

Vinylidene olefins are useful when oligomerized as an oil. According to their viscosity, various uses of the oils are known, for example as lubricants. These materials are mixtures composed of different proportions of higher oligomers in which dimers, trimers, tetramers, pentamers, and oligomers are produced in different proportions in the oligomerization process. In order to increase the viscosity, a method is used in which more higher oligomers are formed or some of the lower oligomers are removed, for example by distillation. The lowest viscosity dimer and trimer products are obtained as a by-product of the production of high viscosity synthetic oils. In order to increase the use of dimers in applications such as low temperature lubricating oils and drilling fluids, there is interest in methods of selectively producing them.

DETAILED DESCRIPTION The present specification, the olefin, "vinyl olefins", i.e. R-CH = CH _2; "vinylidene olefins"
Or below And an internal olefin, wherein the internal olefin is represented by the following formula: “disubstituted olefin” (R ¹ —CH ＝ CH—R),
"Trisubstituted olefin": And "tetrasubstituted olefins": (Wherein R, R ¹ , R ² and R ³ represent a hydrocarbyl group). Further, the internal olefin is the formula: R-CH = as "beta-internal olefinic double bond is attached to the beta carbon atom, as in CH-CH _3, and the following formula: R 1 ^'-CH = Further in olefins as in CH-R ^{2 'where} R ^1' and R ^{2 '} are aliphatic hydrocarbon radicals differing by 2 or 4 carbon atoms and containing more than 2 carbon atoms. It is also classified as a "deep internal olefin" which is a disubstituted olefin in the center direction.

"Beta internal olefin" as referred to herein is a monomer. That is, they contain the same number of carbon atoms as the original vinyl olefin, but the olefin double bond has moved toward the center of the molecule by exactly one carbon number (ie, the double bond is Carbon number).

As used herein, "deep internal olefin" is a dimer of the initial vinyl olefin. For example, the deep internal dimer of 1-octene contains 16 carbon atoms. They differ from vinylidene dimers in that their olefinic double bonds are in a straight chain near the center of the molecule.

The olefins used in making vinylidene olefins are primarily (at least 50% mol%) where olefin unsaturation occurs at the 1- or α-position of the carbon chain.
C ₄ -C ₂₀ straight or branched chain monoolefinically unsaturated hydrocarbon (but not less than 5 mol%). Typically the olefin, the following formula R ² - in _{(CH 2) m -CH = CH} 2 Formula I (wherein, R ² is hydrogen or alkyl, that is, C ₁ -C ₁₆ linear or branched alkyl And preferably C ₁ -C ₆ linear or branched alkyl, most preferably C ₁ -C ₄ linear or branched alkyl, for example methyl or ethyl, m is from 0 to 16
Which is an integer of

Linear α-olefins are commercially available and can be made by pyrolysis of paraffinic hydrocarbons or by known Ziegler ethylene chain formation and substitution by trialkylaluminums. Individual olefins as well as mixtures of said olefins may be used. Examples of the olefin include 1-hexene, 1-heptene,
There are 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-hexadecene and 1-tetra-decene.
More preferred conventional α-olefin monomers are those containing from 8 to 18 carbon atoms.

The olefin monomers can also contain small amounts of internal olefins and vinylidene olefins, ie, 5 to 50%, usually less than 25 mol%. Typically, at least 70% of the olefin monomers have from 8 to 18 carbon atoms.

The α-olefin of formula I is contacted with a catalytically effective amount of a catalyst composition as defined above.

The alkyl aluminum alkoxide catalyst has the formula R ⁴ _n Al
(OR ⁵ ) _p (wherein R ⁴ and R ⁵ are alkyl as defined above, n is a number from 0.75 to 2.75, and p is from 0.25 to 2.2
5 and the sum of n and p is 3).
Therefore, alkyl aluminum alkoxide R ⁴ _1.5 A
l (OR ⁵ ) _1.5 is 1: 1 of R ⁴ Al (OR ⁵ ) ₂ and (R ⁴ ) ₂ AlOR ⁵
It can be a mixture. Compound R ⁴ Al (OR ⁵ ) ₂ is
It can be in small amounts in said mixture, for example R ⁴
_1.95 Al can be 5% in (OR ⁵⁾ _1.05.
Preferably, p is between 0.5 and 1.8.

The alkylaluminum alkoxide can be prepared by methods known to those skilled in the art, i.e., converting the trialkylaluminum to an aliphatic alcohol such as n-butyl alcohol,
n- hexyl alcohol, by reaction with C ₁ -C ₂₀ linear or branched aliphatic alcohols such as n- octyl alcohol, made easier. Alcohol mixtures may be used. Alternatively, the oxidation of the trialkylaluminum may be performed under controlled conditions with air or oxygen.

During dimerization, the catalyst mixture present with the vinyl olefin is from about 0.02 to about 0.3 mole ratio of aluminum to vinyl supplied. If desired, the feed molar ratio
Catalyst concentrations higher than 0.3 may be used, but lower concentrations do not provide the specific advantages. For a typical dimerization reaction designed according to the invention, aluminum /
A catalyst concentration with a vinyl feed molar ratio of 0.04 to 0.20 is preferred.

The dimerization reaction is carried out in a closed container free of air at a temperature that is not low enough to slow down the reaction, but is not too hot, such that the catalytic activity does not decrease due to decomposition of the catalyst. Therefore, it has been found that temperatures between 100 ° C and 250 ° C, preferably between 120 ° C and 200 ° C, most preferably between 120 ° C and 180 ° C are suitable for dimerization.

The alkylaluminum alkoxide mixture that is the catalyst of the present invention is typically pre-made, and may itself be added to the reaction mixture or made in situ. Thus, for example, a mixture of alkylaluminum alkoxide compounds, optionally in an inert solvent,
In addition to vinyl olefins, the dimerization of the present invention may be achieved.

First, the alkylaluminum alkoxide precursor, i.e., the trialkylaluminum, can also be added to the olefin reaction mass with the aliphatic alcohol already present. After a suitable period of time to convert the trialkylaluminum to a catalytically active alkylaluminum alkoxide species (as described herein), the mixture is heated to effect dimerization. .

The most preferred embodiment of the present invention is a process for dimerizing a mixture of olefins containing from 4 to 20 carbon atoms, the majority comprising vinyl olefins and the minority vinylidene and internal olefins. The method includes the formula _{^{R 4 n Al (OR 5)}} p ( wherein, n + p = 3) with is contacted with a schematic of an alkyl aluminum alkoxide represented heating the olefin.

EXAMPLES First of all, 2499 g of 1-decene (molecular weight 140) or 17.8 g
g mol is placed in a 3 liter glass reactor. Next, TNOA (tri-normal octyl aluminum, molecular weight 36
7) Put 218 g or 0.594 g mol in the reactor and add 1
-Mix with decene. The supply molar ratio of aluminum to vinyl is 0.033 (0.594 / 17.8 = 0.033). Then, while stirring the reaction mixture, 38.5 g or 0.296 g mol of n-octanol (molecular weight 130) was added to 1-decene / TNO
Add slowly to the A mixture. There is a release of heat due to the oxidation of TNOA. The degree of oxidation of TNOA is 17% (note that there are three octyl groups attached to the aluminum molecule; therefore, the degree of oxidation is 0.296 / (0.594 × 3) = 17%).

Next, the reaction mixture is raised to the reaction temperature. In this particular example, it is 170 ° C. A sample of the reaction mixture is taken during the reaction, acid washed and analyzed by GC and NMR.

Table 1 shows the composition of the reaction mixture at various times (NMR
% By mol). The results show that the selectivities for beta internal monomer, deep internal dimer, and vinylidene dimer are 9 wt%, 9 wt% and 82 wt%, respectively. The results show that the selectivities for the three components were 15%, 14% and 71% by weight, respectively.
US Pat. No. 4,973,788. Example 6 in U.S. Pat. No. 4,973,788 shows an aluminum / vinyl feed molar ratio of 0.043 and a temperature of 170.
C., without oxidation.

General Procedure A mixture of TNOA, 1-decene and 1-dodecene was prepared at a feed molar ratio of 1/3: 1: 1 (aluminum / vinyl feed molar ratio = 0.1
Prepare in 7). A stoichiometric amount of 1-hexanol is added to the mixture for the corresponding% oxidation of the aluminum alkyl. The reaction between the aluminum alkyl and the alcohol to form aluminum alkoxides and paraffins is quantitative. In experiments, 0%, 11% and
Handles 20% oxidation. The reaction temperatures are 120 ° C, 140 ° C and 160 ° C. The reactor is a glass vessel with a nitrogen blanket.

The progress of the reaction is analyzed by both GC and NMR. G
Analyzes from C and NMR are in agreement. The mol% is obtained from the NMR data. Vinyl is the starting α-olefin monomer. Beta interior is the monomer isomer. Vinylidene and deep internal olefins are dimers. In terms of weight percent, vinylidene and deep internal olefin dimer olefins are much greater than the values expressed in mole percent. The reason is that vinyl and beta internal olefins are monomers.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C07C 2/24 C07C 11/02

Claims (6)

(57) [Claims] [1] The following equation (Wherein R ¹ and R ² are the same or different and are hydrogen or alkyl, m is an integer of 0 to 18, provided that when m is 0, R ² is not hydrogen) A vinylidene olefin of the formula R ⁴ _n Al (OR ⁵ ) _p (wherein R ⁴ and R ⁵ is the same or different and is alkyl, and n is 0.75 to 2.
In the presence of a catalytically effective amount of a catalyst composition having a value of 75, wherein p has a value of 0.25 to 2.25 and the sum of n and p is 3). The method comprising the step of: 2. The method according to claim 1, wherein R ¹ and R ² are hydrogen. 3. The method according to claim 1, wherein R ² is a C ₂ -C ₁₆ branched aliphatic hydrocarbon group. 4. The method according to claim 1, wherein said temperature is 120 ° C. to 200 ° C.
3. The method according to any one of 3. 5. A process for dimerizing a mixture of alpha olefins containing 4 to 20 straight or branched chain carbon atoms, said olefin mixture comprising substantially 50 to 95 weight percent of vinyl olefins. %, 5 to 50% by weight of vinylidene olefin,
And a small amount of an internal olefin, the method comprising:
An aluminum / vinyl feed molar ratio of 0.02 to 0.3 at a temperature of 120 ° C to 180 ° C until a substantial amount of the vinyl olefin dimerizes to form dimerized vinylidene and a deep internal olefin. Heating the olefin mixture in contact with a catalytic amount of an alkylaluminum alkoxide, and wherein the vinylidene olefin formed from the alpha olefin comprises from 8 to 36 carbon atoms. An olefin comprising
The method according to claim 1, wherein the method has the structure shown in claim 1. 6. The method according to claim 5, wherein at least 70% by weight of the alpha olefins in the olefin mixture are octene, decene, dodecene, tetradecene, hexadecene or octadecene.